JPH11181218A - Resin composition for plating use and plated molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a plated molded product made of an improved AES resin- based composition capable of easy plating operation under similar conditions to those for conventional ABS resin plating operation. SOLUTION: The subject resin composition comprises a total of 100 pts.wt. of (A) 10-80 pts.wt. of a graft polymer produced by grafting an aromatic vinyl monomer and vinyl cyanide monomer or another monomer copolymerizable therewith to an ethylene-propylene-based rubber, (B) 10-60 pts.wt. of a graft polymer produced by grafting a (meth)acrylic ester-based or another monomer copolymerizable therewith to a conjugated diene-based rubber 0.1-0.4 μm in weight-average particle size, and (C) 10-80 pts.wt. of a copolymer produced by copolymerization between aromatic vinyl monomer and vinyl cyanide monomer or another monomer copolymerizable therewith. The other objective plated molded product is obtained by plating a resin molded product obtained by molding the above composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a graft polymer obtained by polymerizing an aromatic vinyl monomer and a vinyl cyanide monomer on an ethylene-propylene rubber, so-called A
The present invention relates to a plating resin composition obtained by blending a specific graft polymer having a specific particle diameter with an ES resin, and a plated molded product obtained by plating a resin molded product obtained by molding the resin composition. .

[0002]

2. Description of the Related Art Acrylonitrile-butadiene-styrene resin (ABS resin) has been used in many cases for plating and decoration to give a metallic appearance, and is known as a material which can be plated relatively easily. Have been. In recent years, there has been an increasing demand for plating decoration, and in addition to plating not only on the entire molded product, but also plating on only a part, so-called partial plating, or using plating and painting on the same molded product in the past Specifications that differ from are increasing. In particular, with regard to partial plating, since a part of the resin is exposed on the design surface, the conventionally used AB
Since the S resin has poor weather resistance, there is a problem that the usable environment is limited. For such a problem,
Substitution of a so-called AES resin, which is a resin having excellent weather resistance, in which a butadiene component, which is a rubber component of an ABS resin, is changed to an ethylene-propylene rubber, is being studied. Under the conditions, in the etching step, which is a means for improving the adhesion between the plating metal film and the resin, the etching tends to proceed too much (over-etching), and conversely, a problem such as insufficient etching is likely to occur. At present, it has not been obtained.

[0003]

SUMMARY OF THE INVENTION The present invention relates to a conventional AB
Provided are an improved AES resin composition for plating that can be easily plated under the same conditions as S resin plating, and a plated molded article obtained by plating a resin molded article obtained by molding the resin composition. The purpose is to do so.

[0004]

That is, the present invention provides an aromatic vinyl monomer and a vinyl cyanide monomer or another monomer copolymerizable with these monomers on an ethylene-propylene rubber. 10-80 parts by weight of a graft polymer (A) obtained by polymerizing a monomer and a weight average particle diameter of 0.1-80.
10 to 60 parts by weight of a graft polymer (B) obtained by polymerizing a conjugated diene rubber having a diameter of 0.4 μm with a (meth) acrylate monomer or another monomer copolymerizable therewith; 10 to 80 parts by weight of a copolymer (C) obtained by polymerizing an aromatic vinyl monomer and a vinyl cyanide monomer or another monomer copolymerizable with these monomers (( A) + (B) + (C) = 100 parts by weight) and a plated molded product obtained by plating a resin molded product obtained by molding the resin composition. .

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. As the ethylene-propylene rubber constituting the graft polymer (A) in the present invention, non-conjugated diene components such as ethylene-propylene copolymer rubber, ethylidene norbornene, dicyclopentadiene and 1,4-hexadiene are introduced. Ethylene-propylene-non-conjugated diene copolymer rubber. In particular, ethylene content is 30 to 80% by weight, Mooney viscosity (ML1 + 412
(1 ° C) 40 to 80 is preferred.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, bromostyrene and the like, and one or more of them can be used. Particularly, styrene and α-methylstyrene are preferred. Examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, and the like, and one or more kinds can be used.

In the present invention, as the monomer constituting the graft polymer (A), another monomer copolymerizable with an aromatic vinyl monomer and a vinyl cyanide monomer is used. It is also possible. Examples of such monomers include (meth) acrylate monomers such as methyl methacrylate and methyl acrylate, maleimide monomers such as N-phenylmaleimide and N-cyclohexylmaleimide, acrylic acid, methacrylic acid and the like. Examples thereof include unsaturated carboxylic acids such as acid, itaconic acid and fumaric acid, each of which can be used alone or in combination of two or more.

The above-mentioned aromatic vinyl monomer (i), vinyl cyanide monomer (ii) and other copolymerizable monomers
The composition ratio of (iii) is not particularly limited, but (i) 50 to 50%
95% by weight, (ii) 5 to 50% by weight and (iii) 0 to 4
Preferably it is 5% by weight. The composition ratio of the ethylene-propylene rubber and the monomer (total) is also not particularly limited, but is 10 to 80% by weight of the ethylene-propylene rubber-like polymer and 90 to 2 of the monomer (total).
It is preferably 0% by weight.

The graft ratio of the graft polymer (A) is not particularly limited, but is preferably from 10 to 150%, and particularly preferably from 30 to 100% from the balance between moldability and strength.

The conjugated diene rubber constituting the graft polymer (B) in the present invention includes polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer and the like. The conjugated diene rubber has a weight average particle diameter of 0.1 to 0.4 μm. If the weight average particle diameter is less than 0.1 μm, the etching property in the plating step is poor, and the phenomenon that the plating is not partially fixed (skip) tends to occur, which is not preferable. On the other hand, if the weight average particle diameter is larger than 0.4 μm, it is not preferable because conversely, overetching tends to occur and the adhesion between the plating film and the resin is reduced. The range of 0.20 to 0.30 μm is particularly preferable in terms of plating property and strength.

The (meth) acrylate-based monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid 2 -Ethylhexyl and the like, and one kind or two or more kinds can be used.

Other monomers copolymerizable with the (meth) acrylic ester monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, paramethylstyrene and bromostyrene; Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile;
Maleimide monomers such as phenylmaleimide and N-cyclohexylmaleimide, acrylic acid, methacrylic acid,
Examples thereof include unsaturated carboxylic acids such as itaconic acid and fumaric acid, and particularly preferred are aromatic vinyl monomers and / or vinyl cyanide monomers.

The composition ratio of the (meth) acrylate monomer (i) and the other copolymerizable monomer (ii) is not particularly limited, but (i) 30 to 100% by weight,
(Ii) It is preferably from 0 to 70% by weight. The composition ratio of the conjugated diene rubber and the monomer (total) is not particularly limited, but may be 10 to 80% by weight of the conjugated diene rubber and 90 to 20% by weight of the monomer (total). preferable.

The graft ratio of the graft polymer (B) is not particularly limited, but is preferably from 10 to 150%, and particularly preferably from 20 to 100% from the balance between moldability and strength.

As the aromatic vinyl monomer constituting the copolymer (C) in the present invention, styrene, α-methylstyrene, paramethylstyrene, bromostyrene and the like can be mentioned. Can be. Particularly, styrene and α-methylstyrene are preferred. Examples of the vinyl cyanide-based monomer include acrylonitrile, methacrylonitrile, and the like, and one or more kinds can be used.

In the present invention, it is also possible to use other monomers copolymerizable with the aromatic vinyl monomer and vinyl cyanide monomer constituting the copolymer (C). is there. Examples of such monomers include (meth) acrylate monomers such as methyl methacrylate and methyl acrylate, maleimide monomers such as N-phenylmaleimide and N-cyclohexylmaleimide, acrylic acid, methacrylic acid and the like. Examples thereof include unsaturated carboxylic acids such as acid, itaconic acid and fumaric acid, each of which can be used alone or in combination of two or more.

The above-mentioned aromatic vinyl monomer (i), vinyl cyanide monomer (ii) and other copolymerizable monomers
The composition ratio of (iii) is not particularly limited, but (i) 50 to 50%
95% by weight, (ii) 5 to 50% by weight and (iii) 0 to 4
Preferably it is 5% by weight.

Further, the intrinsic viscosity of the copolymer (C) (30
C, dimethylformamide) is not particularly limited,
It is preferably from 0.4 to 1.0.

The method for polymerizing the graft polymers (A) and (B) and the copolymer (C) used in the present invention is not limited, and may be a known emulsion polymerization method, bulk polymerization method, solution polymerization method, or the like. A suspension polymerization method or a method in which these polymerization methods are arbitrarily combined can be employed.

The resin composition of the present invention comprises 10 to 80 parts by weight of the above graft polymer (A) and 10 parts by weight of the graft polymer (B).
６０60 parts by weight and 10 to 80 parts by weight of the copolymer (C) ((A) + (B) + (C) = 100 parts by weight).
If the mixing ratio of the resin composition is out of the range, good plating properties cannot be obtained, which is not preferable. Further, the proportion of the rubber component derived from the component (A) and the component (B) in the resin composition is preferably from 10 to 40% by weight, and when the proportion is less than 10% by weight, the strength of the molded article is low. When the content is less than 40% by weight, the moldability tends to be reduced and the film tends to be over-etched, and the adhesion between the plating film and the resin is undesirably reduced.

In the resin composition of the present invention, if necessary,
Other resins such as polycarbonate, polyester, polyphenylene ether and polyamide, various additives such as colorants, dispersants, antioxidants, ultraviolet absorbers, flame retardants, etc., or various reinforcing materials such as glass fiber, carbon fiber and calcium carbonate Etc. can be added. The mixing of the resin composition of the present invention can be carried out by a commonly used method such as a roll, a Banbury mixer, an extruder, or a kneader.

The resin composition thus obtained is molded by injection molding, extrusion molding, compression molding, injection compression molding, blow molding, or the like. The plating process is performed under the same conditions as the plating conditions of the ABS resin.

[Examples] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the examples, parts and percentages are based on weight.

-Graft polymer (A)-A-1: Ethylene-propylene-ethylidene norbornene rubber (ethylene content 60% by weight, Mooney viscosity 6)
5) 50 parts by weight, 35 parts of styrene and 15 parts of acrylonitrile were graft-polymerized by a known solution polymerization method to obtain a graft polymer (A-1).

-Graft polymer (B)-B-1: 50 parts of styrene-butadiene copolymer rubber (weight average particle diameter 0.25 μm), methyl methacrylate 45
Parts and 5 parts of ethyl acrylate were graft-polymerized by a known emulsion polymerization method to obtain a graft polymer (B-1). B-2: polybutadiene rubber (weight average particle size 0.40
μm) 60 parts, methyl methacrylate 25 parts, styrene 1
0 parts and 5 parts of acrylonitrile were graft-polymerized by a known emulsion polymerization method to obtain a graft polymer (B-2). B-3: polybutadiene rubber (weight average particle size 0.30
μm) 40 parts, 45 parts of methyl methacrylate and 15 parts of acrylonitrile were graft-polymerized by a known emulsion polymerization method to obtain a graft polymer (B-3). B-4: polybutadiene rubber (weight average particle size 0.20
μm), 50 parts of methyl methacrylate, and 30 parts of styrene were graft-polymerized by a known emulsion polymerization method to obtain a graft polymer (B-4). Bi: polybutadiene rubber (weight average particle size 0.05
μm), 50 parts of methyl methacrylate and 30 parts of styrene were graft-polymerized by a known emulsion polymerization method to obtain a graft polymer (B-i). B-ii: polybutadiene rubber (weight average particle size 0.50
μm), 50 parts of methyl methacrylate, 30 parts of styrene and 20 parts of styrene were graft-polymerized by a known emulsion polymerization method to obtain a graft polymer (B-ii). B-iii: polybutadiene rubber (weight average particle size 0.40
μm), 50 parts of acrylonitrile and 35 parts of styrene were graft-polymerized by a known emulsion polymerization method to obtain a graft polymer (B-iii).

-Copolymer (C)-C-1: 75 parts of styrene and 25 parts of acrylonitrile are polymerized by a known bulk polymerization method to obtain a copolymer (C-1).
I got

Examples 1 to 7 and Comparative Examples 1 to 4 The above graft copolymer (A-1) and graft copolymer (B
-1 to 4, B to i to iii) and the copolymer (C-1) were mixed at the compounding ratio shown in Table 1, and melt-mixed at 230 ° C. using a 40 mm twin-screw extruder to form pellets. A molded article for plating (100 × 50 × 3 mm) was molded by an injection molding machine, and the light resistance of the obtained molded article was measured. Further, plating was performed by the following method to obtain a plated molded product. Each characteristic was measured by the following methods. Table 1 shows the results.

Plating process: degreasing (surfactant aqueous solution, 55 ° C. × 3 minutes), etching (sulfuric acid-chromic anhydride mixed solution, 65-70 ° C. × 15 minutes), neutralization (hydrochloric acid aqueous solution, room temperature × 3 minutes) , Catalyst (palladium chloride-stannous chloride-hydrochloric acid aqueous solution, room temperature x 2 minutes),
Accelerator (sulfuric acid aqueous solution, 45 ° C x 3 minutes),
Electroless plating (nickel plating solution mainly composed of nickel sulfate-sodium hypophosphite-sodium citrate), electroplating (copper sulfate bath → nickel sulfate bath → chromic anhydride bath)

O Surface gloss after etching: After the etching, the surface gloss (%) was measured with a handy gloss meter (Gloss Checker IG-310 manufactured by Horiba, Ltd.). o Peeling strength: Based on JIS H-8630, adhesion strength of plating film (indicated by stress when a metal film of a plated product is cut at 1 cm intervals reaching the substrate and peeled off in a vertical direction) ) Was measured (kg / c
m ² ). o Molded product appearance: The appearance after plating (no plating) was visually judged according to the following criteria. ；: Good plating with plating on the whole. Δ: Slightly inferior in a part without plating. ×: defective in a state where plating was not applied. o Light fastness: Test piece for light fastness measurement (100 × 50 × 3 m
m) at 63 ° C. using FOM (manufactured by Suga Test Instruments)
After performing the light resistance test for 0 hours, (ΔE) of the test piece was measured by a color difference meter (manufactured by Suga Test Instruments).

[0030]

[Table 1]

[0031]

The resin composition according to the present invention is an AES-based resin composition having excellent weather resistance, and has excellent plating properties which can be easily plated under the same conditions as conventional ABS resin plating. It can be used without being limited to the environment (outdoor) even if it is partially plated,
It can be effectively used as various plating products.

Claims (2)

[Claims] 1. A graft weight obtained by polymerizing an ethylene-propylene rubber with an aromatic vinyl monomer and a vinyl cyanide monomer or another monomer copolymerizable with these monomers. Combined (A) 10 to 80 parts by weight, conjugated diene rubber having a weight average particle diameter of 0.1 to 0.4 μm, a (meth) acrylate monomer or another monomer copolymerizable therewith Polymer (B) obtained by polymerizing a polymer
10 to 60 parts by weight of an aromatic vinyl-based monomer and a vinyl cyanide-based monomer or a copolymer (C) obtained by polymerizing these monomers with another monomer copolymerizable therewith ~
80 parts by weight ((A) + (B) + (C) = 100 parts by weight)
A plating resin composition comprising: 2. A plated molded article obtained by plating a resin molded article obtained by molding the resin composition according to claim 1.